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Zhang, J. Chem. Soc. Rev. 2015, 44, 677. (f) Fensterbank, L.; Malacria, M.
trapped by the more nucleophilic indolyl to form intermediate D2
by overcoming a barrier of 5.0 kcal/mol. Finally, intermediate D1
or D2 was readily converted into product 3a or 5a through proton
transfer11 and ligand exchange, and 5a could be further converted
into product 6a through dehydrogenative oxidation.
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Zhao, T.; Zhang, W.; Lu, X.; Ye, L.-W. Chem. Sci. 2015, 6, 1265. For a
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In summary, the challenging generation of α-imino gold
carbenes via gold-catalyzed intermolecular reaction of azides and
alkynes has been achieved, leading to the site-selective synthesis
of versatile 2-aminoindoles and 3-amino-β-carbolines in generally
good to excellent yields. In addition, a mechanistic rationale for
the observed regioselectivity is also strongly supported by DFT
computations. In comparison with the intermolecular alkyne
oxidation approach to the generation of gold carbenes, this
strategy is not only more atom-economic, but also more flexible
as it can introduce various amino groups while only the oxygen is
transferred in case of the related oxidation approach. The tandem
process facilitates the assembly of complex heterocyclic structures
from readily assembled alkyne starting materials. Further
application of this gold-catalyzed intermolecular alkyne amination
will be pursued in our laboratory.
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ASSOCIATED CONTENT
Supporting Information
Experimental procedures and characterization data. This material
AUTHOR INFORMATION
Corresponding Author
(10) (a) Li, L.; Zhou, B.; Wang, Y.-H.; Shu, C.; Pan, Y.-F.; Lu, X.; Ye,
L.-W. Angew. Chem., Int. Ed. 2015, 54, 8245. (b) Li, L.; Shu, C.; Zhou, B.;
Yu, Y.-F.; Xiao, X.-Y.; Ye, L.-W. Chem. Sci. 2014, 5, 4057. (c) Pan, F.;
Liu, S.; Shu, C.; Lin, R.-K.; Yu, Y.-F.; Zhou, J.-M.; Ye, L.-W. Chem.
Commun. 2014, 10726.
ACKNOWLEDGMENT
We are grateful for the financial support from the NNSFC
(21272191 and 21273177), NSFFJ for Distinguished Young
Scholars (2015J06003), PCSIRT, NFFTBS (J1310024) and
SRFDP (20130121110004).
(11) For details, please see the Supporting Information (SI).
(12) For a gold- or silver-catalyzed intramolecular cyclization of 2-
alkynyl benzyl azides, see: (a) Huo, Z.; Yamamoto, Y. Tetrahedron Lett.
2009, 50, 3651. (b) Niu, Y.-N.; Yan, Z.-Y.; Gao, G.-L.; Wang, H.-L.; Shu,
X.-Z.; Ji, K.-G.; Liang, Y.-M. J. Org. Chem. 2009, 74, 2893.
(13) For the structures of compounds 3ah', 3o' and 6r', see as followed:
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